ALDRIDGE GROUP

N-HETEROCYCLIC

CARBENES

Anion-functionalized NHCs (NP)

Air-stable 14-electron Ir(III) (NP)

NHC gold hydride (also NP)

(Recent work from Nick Phillips)

N-heterocyclic carbenes (NHCs) are neutral, strongly donating ligands which have been widely exploited in the stabilisation of cationic metal species implicated in homogenous catalysis. Within the Aldridge group we have an interest not only in developing novel NHCs with tailored electronic, steric and solubility properties, but also in exploiting these ligand systems in the stabilization of highly electrophilic Main Group and Transition Metal complexes.

Anionic NHCs: We have recently developed a versatile methodology for the synthesis of anionic NHCs featuring a 5-, 6-, or 7-membered saturated heterocyclic core. Lewis acid promoted exocyclic ring closure generates systems in which a pendant borate or aluminate functionality is incorporated via a CH2 linker. This allows for electronic and steric isolation of the anionic component; hence a library of NHCs can be accessed which incorporate metal binding environments essentially identical to the neutral parent donors, but with significantly altered solubility profiles.

Gold and iridium complexes: Expanded ring NHCs (those based on a heterocycle with >5 atoms) have proved to be extremely apt at stabilizing highly electrophilic late Transition Metal complexes: the strongly sigma donating and sterically shielding nature of such ligands have allowed for the isolation of 14-electron Ir(III) systems and highly reactive Au(I) compounds of potential catalytic relevance.

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Copyright S Aldridge

2016

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